Azo dyestuffs and material dyed therewith



Patented May 13, 1930 UNITED STATES WEI-HELL! m1, 0]? FRANKFORT-ON-THE-MAIN-HOGHST, ANIO WERNER KIRST, OE

mmOBT-ON-THE-MAIN, GERMANY,

ASSIGNORS TO GENERAL ANILINE WORKS,

INC.-, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE AZO DYESTOFFS AND IA'IERIAL DYED TH EBEWITH Io Drawing. Application filed December 3, 1928, Serial No. 323,555, and in Germany December 10, 1927.

The present invention relates to azo dyestufis and material dyed therewith.

We have found that claret, violet and violet-brown azo dyestufis are obtained by diazotizing a 4amino-naphthalic acid derivative of the follo constitution:

N 00 to I V N v 0.NH-aryl Y Y I wherein X stands for hydrogdji alkyl aryl or aralkyl and wherein the 1 residue may free sulfonic or carbox yl ic group and Y stands for hydrogenor for the residue:

wherein X has the same meaning as in the I preceding formula.

The l-aminonapht halic acid derivatlves may for instance be prepared from the 4- aminonaphthalic anhydride or a substitution product thereof by decomposing it with ammonia, with analiphatic or aromatic amine.

The following examples serve to illustrate our invention, but they are not intended 0 limit it thereto.

1. (a) 50 grammes of boiled cotton-yarn are treated for about hour with thefol lowing grounding liquor: 4.5 grammes of 2.3-hydroxynaphthoic acid-2'.5'-dimethoxyl'-anilide, 9 com. of Turkey 'red oil and 9 cc.

of caustic soda solution of 34 B. are. disi solved While boiling in hot water and the whole is made up to 1000 cc. Then 4.5 cc. of

formaldehyde of 30% strength are added.

(6) The impregnated yarnis well freed from water and developed in a diazo solution prepared in the following manner:

2.2 grammes of 4-amino'-1.8-naphthal-- 40 be substituted or not, but must contain no methylimideare made into a paste with taken out, well mixed, soaped at boiling temstrength;

of hot water and diazotized by means of 7.5

cc. of sodium nitrite dissolved in water in the proportion of 1. 10.

' The .diazoti za'tionbeing completed, the whole is neutralized with about 2 grammes of sodium acetate,,diss olved in water, so as tion from 4-amino-1.8-naphthalmethylimide" and'further treated as indicated in :Example' 1'. A violet brown of very good fastness to light is obtained. Thedyestuffs has the fol-.-

to indicate :neutral reaction towards-Congo paper, 25 grammesof sodium chlorlde are .added and the liquor-is made up with cold spring'water to 1 liter. 1

After about hours dyeing, the yarn is perature, again rinsed and dried. v

A beautiful, very bluish claret dyeing is obtained of excellent fastness to light. The r dyestufl has the following formula:

A OO

2: 50 grammespf boiled' cotton yarn are treated with the following grounding liq- 4 J of 2.3-hydroxynaphth'oi acid 1-naphtl;yl'amide, 8 cc. of Turkey.red oil, 12 cc. ofcaus'tic soda solution of 34.? B. are dissolved while boiling in hot water and the whole is made up to 1000 'cc. Then there are added 4 cc. of formaldehyde of 30% The whole is developed with a diazo solution from 4-amino-1.S-naphthalmethylimide, the developed dyeing is treated as indicated in Example 1 and a beautiful, blue Bordeaux dyeing of very good fastness to light is obtained. The dyestufi has the following formula:

3. 50" grammes of boiled cotton yarn are :011 v co-Nn treated with the following bath: 2 grammes of di-2.3-hydroxynaphtho1c aciddianisidide, 10 cc. of Turkey redoil of 50% strength and 6 cc. of caustic-soda solution of 34 B. are dissolved .in boiling water and the whole'is made up to 1 liter.

lowing formula:

-The dyeing is developed with a diazo solu-' 4. 50 grammes of boiled cotton yarn naphthoic acid 2 .5 dimethoxy-1'-anilide and dyed in the following bath:' t 2.06 grammesv of 4- amino-'1.8-naphtha lamide are diazotized in the cold with 2.8 cc. of

hydrochloric acid of 22 B. and 7.5 cc. of

a solution of sodium nitrite in water c0n-- taining 1 g. in 10 cc. After the diazotization is complete, the mass is neutralized with about 2 grammes of dissolved sodium acetate so that it gives a neutral reaction with Congo paper and the whole is made up with addition of 25 grammes ofsodium chloride to.-1

liter. After having developed for about hour,'the yarn is rinsed,-"Isoaped at boiling temperature and dried. A beautiful claretred dyeing of excellent fastness to light is obtained. The dyestufi has the following formula w izs treated with the following grounding liqnor: 7 grammes of 2.3-hydroxynapthoic acid .anilide, 14 cc. of Turkey red oil of 50% 6. 50 grammes of boiled cotton yarn are treated in a solution of 4 grammes of 2.3- hydroxynaphthoic acid 1 naphthylamide (prepared according to Example 2 and developed-with a diazo solution prepared ac cordmgto Example 4). The material is soaped at boiling temperature, rinsed anddried. A violet tintof good fastness to light is obtained. The dyestuif hasthe following formula:

.. C O-NH8 7. 5O grammes of boiled cotton yarn are impregnated with the following naphthol solution: 4.5 grammes of 2.3-hydroxy-naphthoic acid-4'methoxy-1 '-anilide are dissolved in boiling water together with 9 cc.

of Turkey red oil of 50% strength and 9 cc. of caustic soda solution of 34 B6. and the whole is made up to-l liter. Then there are added 4.5 cc. of formaldehyde of 30% strength. The naphtholated yarn is developed in a diazo solution prepared according to Example 4 from 4-amino-L8-naphthalimide and after-treated in the above indicated manner. A violet tint of good to very good fastness to light isobtained. The dyestuff has the following formula:

OKXO

8. 5O grammes of boiledcotton-yam are treated with a grounding liquor prepared as indicated in Example 3 from 2-gramms of di 2.3 hydroxynaphthoic acid-dianisidide. Then the dyeing is developed in a diazo solution prepared according to Example 4 from 4-amino-1.8-naphthalimide, rinsed, soaped at boiling temperature, dried and a chocolate brown tint of very good fastness to light A is obtained. The dyestuif has the following formula:

The following table illustrates a number of the dyestuffs obtained according to the examples, but it is not to lac-understood as limiting the possibility to obtain similar dyetilcoupling component, than those included in lent fastness to light.

. stufls of equally good fastness properties by let or violet-brown dyestuffs of good fastness some other combinations of the base and the to washing and chlorine and good to excel-- the table. 2. As new products, azo dyestufis of the Combinedwith m2, snowing arylamide shade of. the Diazo compound from of 2.3-hydroxynaphthoic acid dyeing (1) 4-amino-1.8-naphthalimlde 2'-m'ethoxy-1'-anilide Bordeaux (2) 4-amino-1.8naphthalethy1imide 25-dimeth0xy,-1'-anilide Bluish-Bordeaux (3) 4-amino-1.8-naphthalethy1lmide 2'-methoxy-,1-anilide Bordeaux (4) 4-amino-1.S-naphthalethylimide 4'-methoxy-1'-auilide Bordeaux (5) 4amino'1.S-uaphthalphenyllmide 2'5'-dimethoxy-1'-anilide Violet (6) -amlno-l.8-naphthal-para-tolyllmide 2-'5'-dimethoxy-1-anilide Bluish-Bordeaux (7) 4-am1n0-1.S-naphthal-meta-tolylimide 25'-dimethoxy-1'-auilide Bordeaux (8) 4-amino-L8-naphthal-meta-metadimethyl-phenylim- 25'dimethoxy-1-anilide ide I e Reddish-violet (9) 4-:1miuo-1.8-naphthal-ortho-ortho-dimethyl-phenylim- 2'5'-dimethoxy-1'-ani1ide ide Bordeaux (10) 4-amino-1.8-naphthal-orthoortho-dimethyl-pheny]im- 2'-methoxy-1-anilide ide v Bordeaux (11) 4-amino-L8-naphthal'ortho-ortho-dimethyl-phenylim- 4-methoxy1-anilide ide Bordeaux 12) 4-amino-l.8-naphthalorthmchlorophenylimide 2'5'-dimethoxy-1'-anilide Bordeaux (13) 4-amin0-1;8-naphthal-orth0-chlorophenylimide 4-methoxy-1'-anilide Reddish-Vmlct (14) 4-amino-L8-uaphthal-ortho-chlorophenylimide 2'-methoxy-1 '-ani1ide Bordeaux We claim: following formula.- 1. As new products, azo dyestufis of the X followlng formula: 06 (40 N V i 106 E0 OH OH ONH-aryl wherein X stands'for hydrogen, alkyl, aryl J or aralkyl and wherein the aryl residue may be substituted or not, but must contaln no wherein X' stands for hydrogen, all (yl, aryl or aralkyl, and wherein the aryl residue may be substituted or not but must contain no free sulfonic or carboxylic group and Y stands for hydrogen or the residue wherein X has the same meaning as in the wherein X stan precedingformula, being claret, garnet, viowherein the ary free sulfonic or carboxylic group, being claret, garnet or violet dyestuffs of good fastness to washing and chlorine and good to excellent fastne ss to light.

-3. As new products, azo dyestufis of the ',1, or! do for hydrogen or 'alkyl and l residue may be substituted and chlorine and or not, but must contain no free sulfonic or carboxylic group, being claret, garnet or violet dyestuffs of a good fastness to washing good to excellent fastness to light.

4. As new products, azo dyestuffs of the following formula:

wherein the aryl residue maybe substituted or not, but must contaln no free sulfon c or carboxylic group, belng claret, garnet or V10- let dyestuffs of a good fastness to washing and chlorine and good'to excellent fastness to light.

5. As new products, azo dyestuffs of thefollowing formula:

I co Y CMHQ Y wherein X stands for hydrogen, alkyl, aryl or aralkyl and Y stands for hydrogen orv OCH being violet, garnet, and claret shades of good fastneslsto washing and chlo-- rine and good to excellent fastness to light. 6. As new products, azo dyestuffs of the following formula: I

r oa a Y o O-NHQ Y wherein X stands for hydrogen or alkyl and Y stands for hydrogen or OCH being bluish claret, violet or garnet dyestuffs of good fastness, especially good to excellent fastness to light.

7. As new products, azo dyestuffs of the following formula:

i oft-O oons c O-NH-Q wherein X stands for hydrogen, alkyl, aryl or aralkyl, being garnet, and bluish claret shades of good fastncss to Washing and chlorine and very good to excellent fastness to light.

9. As new products, azo dyestuffs of the following formula: e r

I OCH: oo-NHQ 0H1 gc'la-imedin claim 9 w l 20. Material-dyed with the V dyestuffas tures,

wherein X stands for hydrogen or alkyl, being garnet and bluish claret shades of good fastness to washing and chlorine andexcellent fastness to light. g

10. As a new product, the azo dyestufl of the following formula: v

being water-insohihleland dyeing the mate- -rial a bluish claretsliade of good fastness to y 25 washing and chlorine and excellent fastness to light.

11. Material, dyed with "dyestuffs as claimed in claim 1; I l "12rMaterial' dyed with dyestufi's as claimed in claim 2. V 1

13. Material dyed. withdyestufi's as claimed in claim 3. 14; Material. dyed with dyestufis as claimed in claim 4. y

15. Material dyed with dyestufi's as claimed in claim5.

16. Material dyed with dyestuffs as claimed i-n-claim-6 17. Material 'dyed with dyestuffs as, claimed in claim 7.

18., Material dyed with dyestufis as a claimed in claim 8. l' V v 19. Material dyed with dyestufis as claimed in claim 10. 7 a r In testimonywhereof, we afiix our signa- ECKERT. -WERNER KIRST. 

